CN112830682A - Glass material for solar cell conductive paste and preparation method and application thereof - Google Patents
Glass material for solar cell conductive paste and preparation method and application thereof Download PDFInfo
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- CN112830682A CN112830682A CN202011503933.4A CN202011503933A CN112830682A CN 112830682 A CN112830682 A CN 112830682A CN 202011503933 A CN202011503933 A CN 202011503933A CN 112830682 A CN112830682 A CN 112830682A
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- Prior art keywords
- glass
- glass frit
- frit
- solar cell
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Links
- 239000011521 glass Substances 0.000 title claims abstract description 304
- 239000000463 material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000002844 melting Methods 0.000 claims abstract description 44
- 230000008018 melting Effects 0.000 claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 18
- 239000010703 silicon Substances 0.000 claims abstract description 18
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 15
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910020222 Pb—Si Inorganic materials 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 39
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 32
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 claims description 21
- 239000002994 raw material Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 19
- 238000010791 quenching Methods 0.000 claims description 13
- 230000000171 quenching effect Effects 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 9
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 9
- 229910052749 magnesium Inorganic materials 0.000 claims description 9
- 239000011777 magnesium Substances 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 6
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 6
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 6
- 101001073212 Arabidopsis thaliana Peroxidase 33 Proteins 0.000 claims description 5
- 101001123325 Homo sapiens Peroxisome proliferator-activated receptor gamma coactivator 1-beta Proteins 0.000 claims description 5
- 102100028961 Peroxisome proliferator-activated receptor gamma coactivator 1-beta Human genes 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000013078 crystal Substances 0.000 claims description 5
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 4
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000464 lead oxide Inorganic materials 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 3
- 238000011049 filling Methods 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 9
- 108700024661 strong silver Proteins 0.000 abstract description 3
- 238000013329 compounding Methods 0.000 abstract 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 68
- 229910052709 silver Inorganic materials 0.000 description 51
- 239000004332 silver Substances 0.000 description 51
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 26
- 239000002002 slurry Substances 0.000 description 24
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 17
- 238000000227 grinding Methods 0.000 description 16
- 238000005245 sintering Methods 0.000 description 12
- 239000000843 powder Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 235000012431 wafers Nutrition 0.000 description 10
- 230000008569 process Effects 0.000 description 9
- 239000012074 organic phase Substances 0.000 description 8
- 239000001856 Ethyl cellulose Substances 0.000 description 7
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 7
- 229910003069 TeO2 Inorganic materials 0.000 description 7
- 229920001249 ethyl cellulose Polymers 0.000 description 7
- 235000019325 ethyl cellulose Nutrition 0.000 description 7
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- FUWDFGKRNIDKAE-UHFFFAOYSA-N 1-butoxypropan-2-yl acetate Chemical compound CCCCOCC(C)OC(C)=O FUWDFGKRNIDKAE-UHFFFAOYSA-N 0.000 description 6
- NQBXSWAWVZHKBZ-UHFFFAOYSA-N 2-butoxyethyl acetate Chemical compound CCCCOCCOC(C)=O NQBXSWAWVZHKBZ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229910018530 Si-Ag Inorganic materials 0.000 description 5
- 229910008383 Si—Ag Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000019353 potassium silicate Nutrition 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 150000003497 tellurium Chemical class 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000000075 oxide glass Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910017982 Ag—Si Inorganic materials 0.000 description 1
- 229910004205 SiNX Inorganic materials 0.000 description 1
- XNRNVYYTHRPBDD-UHFFFAOYSA-N [Si][Ag] Chemical compound [Si][Ag] XNRNVYYTHRPBDD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(III) oxide Inorganic materials O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910021419 crystalline silicon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000000156 glass melt Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B19/00—Other methods of shaping glass
- C03B19/10—Forming beads
- C03B19/1005—Forming solid beads
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
- C03C8/245—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders containing more than 50% lead oxide, by weight
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
The invention discloses a glass frit for solar cell conductive paste, which is a mixed glass frit consisting of A, B, C three types of glass, wherein A type is a Pb-Si glass system without tellurium and bismuth; the B type is a lead-free Si-Te-Li glass system; class C is a Te-Bi-W glass system that is lead and silicon free. Also discloses a preparation method and application thereof. The class-A glass material without tellurium and bismuth has a relatively high softening point, and provides good open-circuit voltage and tensile force; the B glass has moderate softening point and better corrosion capability, and provides better contact capability and filling factor; the C-type glass has a lower softening point and better fluidity, and further provides better contact capability; by compounding A, B, C three types of glass frits, the silver-melting conductive paste has strong silver melting capability and simultaneously ensures higher open pressure, lower contact resistance and higher bonding strength, so that the conductive paste prepared by the silver-melting conductive paste and the solar cell can achieve higher cell conversion efficiency and high tensile force.
Description
Technical Field
The invention belongs to the technical field of conductive paste, and particularly relates to a glass material for solar cell conductive paste, a preparation method of the glass material, conductive paste prepared from the glass material and application of the conductive paste.
Background
The front silver electrode of the solar cell is an important component for realizing photo-generated current collection, and the front silver paste accounts for 10% -20% of the cost of the whole solar cell, but the contact resistance and the grid line resistance caused by the front electrode account for half of the whole series resistance. In addition, the front electrode gridlines also cause incident light shading losses, resulting in cell fill and efficiency degradation. Therefore, the conductive paste of the high-efficiency solar cell is the key for improving the conversion efficiency of the cell.
As a bonding phase of the conductive paste, the glass frit is not only bonded to the silicon substrate during the sintering process, but also is an important factor in determining contact resistance, surface etching reaction, and the performance of the entire cell, which requires the glass frit to have good electrical and mechanical properties. In addition, the type and amount of the glass powder also have great influence on the open circuit voltage and the filling factor of the slurry under the high-temperature sintering condition. When the sintering temperature is higher than 600 ℃, the glass powder is melted and liquefied and corrodes the SiNx antireflection film layer, silver particles are dissolved in liquid glass solution through contact, the liquid glass solution plays a role of a medium for silver-silicon contact, the silver particles are separated out and precipitated in the cooling process, and inverted pyramids are formed on the surface of the silicon substrate, so that good Ag-Si ohmic contact is formed.
The front silver paste glass powder commonly used at present is Pb-Si system glass powder, PbO components in the glass system are easy to burn through PN junctions, and if the content of PbO is too high, a substrate is corroded more uniformly, a corroded surface becomes smoother, and the bonding strength is reduced; the SiO2 component acts as a network former, providing a denser network structure, with higher amounts significantly increasing the softening point of the glass. The tellurium series glass has good flowing capability and silver melting capability, silver particles are precipitated during the cooling process to form good ohmic contact, and lower contact resistance is provided, so the tellurium series glass is more and more applied to the conductive paste, but the content of TeO2 is too much, so the glass is easy to flow and spread on a Si substrate.
Higher conversion efficiency of the solar cell needs to obtain better open voltage, contact resistance and filling factor at the same time, but the pure improvement of the open voltage is usually accompanied by the sacrifice of partial contact performance, so that the good contact performance is obtained and the good filling factor is ensured at the same time. Therefore, it is important to design a glass frit for conductive paste of a solar cell to balance the open-circuit voltage, contact resistance, fill factor and other properties of the conductive paste and to have high adhesive strength.
Disclosure of Invention
The invention provides a glass material for solar cell conductive paste, which can overcome the defects in the prior art.
The technical scheme of the invention is as follows:
a glass material for solar cell conductive paste is a mixed glass material composed of A, B, C three types of glass, wherein A type is a Pb-Si glass system without tellurium and bismuth; the B type is a lead-free Si-Te-Li glass system; class C is a Te-Bi-W glass system that is lead and silicon free.
The class-A glass frit without the tellurium and bismuth has a high softening point, and provides good open-circuit voltage and tensile force; the B glass has moderate softening point and better corrosion capability, and provides better contact capability and filling factor; class C glasses have a lower softening point and better flow properties, further providing better contact ability. The A, B, C three-class glass matched mixed glass material has strong silver melting capability and ensures higher open pressure, lower contact resistance and higher bonding strength, so that the conductive paste prepared by the material and the solar cell can achieve higher cell conversion efficiency and high tensile force.
In some embodiments, the mixed glass frit comprises 30% to 70% of the total mass of the mixed glass frit by group a glass frit, 20% to 60% of the total mass of the mixed glass frit by group B glass frit, and 5% to 40% of the total mass of the mixed glass frit by group C glass frit.
In some embodiments, the glass frit of group A contains, in terms of oxide, 20 to 60 mol% of silicon oxide, 25 to 80 mol% of lead oxide, and 2 to 10 mol% of lithium oxide.
In some embodiments, the B-based glass frit contains, in terms of oxide, 10 to 50 mol% of silicon oxide, 2 to 24 mol% of tellurium oxide, and 5 to 30 mol% of lithium oxide.
In some embodiments, the C-based glass frit has a tellurium oxide content of 90 to 95 mol%, a bismuth oxide content of 2 to 8 mol%, and a tungsten oxide content of 1 to 7 mol% in terms of oxides.
In some embodiments, the group a glass or the group B glass further comprises one or any of the oxides of zinc, tungsten, sodium, aluminum, copper, magnesium, or salts thereof; preferably, the total amount of the oxides of zinc, tungsten, sodium, aluminum, copper, magnesium or salts thereof is 0 to 42 mol%.
In some embodiments, the group C glass further comprises one or any of the oxides of zinc, lithium, sodium, aluminum, copper, magnesium, or salts thereof; preferably, the total amount of the oxides of zinc, lithium, sodium, aluminum, copper, magnesium or salts thereof is 0 to 8 mol%.
The invention also provides a preparation method of the glass frit for the solar cell conductive paste, which comprises the following steps: the material is prepared by a high-temperature melting quenching method or a sol-gel method;
preferably, the preparation method as described above comprises: preparing raw materials according to the composition of the glass material for the solar cell conductive paste, uniformly mixing the raw materials, melting at 900-1200 ℃ for 20-60 min, quenching, ball-milling, and drying to obtain the glass material.
The invention also provides a solar cell conductive paste, which comprises the mixed glass or the glass frit prepared by the preparation method, wherein the content of the mixed glass frit is controlled to be 1-6% by mass.
The invention also provides the glass material for the solar cell conductive paste, or the glass material prepared by the preparation method, or the application of the solar cell conductive paste in the preparation of single crystal PERC silicon wafers, double-sided aluminum oxide single crystal silicon wafers, the preparation of fine grids by single printing or the preparation of fine grids by step printing.
The invention also provides a solar cell prepared from the conductive paste.
Compared with the prior art, the invention has the following beneficial effects:
the conductive paste prepared from the glass frit has high open-circuit voltage and filling factor and low contact resistance, and a solar cell prepared from the conductive paste has excellent electrical property and high tensile force.
Of course, it is not necessary for any product in which the invention is practiced to achieve all of the above-described advantages at the same time.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to provide technical solutions of the present invention. The technical solution, its implementation and principles, etc. will be further explained as follows.
The glass frit used by the conductive paste of the crystalline silicon solar cell has low melting point and low glass transition temperature, and the glass frit used as a high-temperature bonding phase ensures the bonding strength between the metal thick film and the silicon substrate and promotes the sintering of the silver powder. Firstly, the erosion effect of the glass powder on the antireflection film can ensure that good mechanical contact is obtained; secondly, the glass powder is a medium substance of silver recrystallization on the surface of the silicon emitter, and can obtain approximate ideal Ag/Si ohmic contact at the temperature of an Ag/Si eutectic point; finally, the glass powder can also dissolve silver powder and even influence the sintering kinetic process of the silver powder. Therefore, the glass powder in the silver paste is a main factor for determining the degree of silicon surface erosion, the magnitude of contact resistance and the final electrical performance.
Pb-Si glass is currently the main commercial glass system, but as the PbO content increases, the bonding strength between the electrode and the substrate decreases, the substrate is more uniformly corroded, and the corroded surface becomes smooth, resulting in a decrease in bonding strength. Tellurium is used as a network forming body in the glass component, can increase the dissolution amount of the glass to silver, reduce the contact resistance, and can inhibit the precipitation of silver in the temperature reduction stage of sintering, thereby widening the sintering window and inhibiting the semiconductor substrate from being excessively corroded.
The invention compounds the Pb-Si glass system and B, C tellurium series glass, wherein, the A type glass has higher softening point and provides better open circuit voltage and pulling force; the B glass has moderate softening point and better corrosion capability, and provides better contact capability and filling factor; class C glasses have a lower softening point and better flow properties, further providing better contact performance. By mixing and matching A, B, C three types of glass, the softening point of B, C two types of tellurium-containing lead-free glass is properly adjusted, so that higher bonding strength, a denser grid line structure, lower contact resistance and higher open-circuit voltage can be obtained, and the solar cell has the best performance.
The A-type glass does not contain tellurium and bismuth with low melting points and contains much SiO2The components have poor fluidity, so that the glass has a higher softening point and an open-circuit voltage, a certain amount of PbO is added to form a low eutectic system, a uniform and stable glass state can be formed at a lower temperature, but the content of PbO is not too high, otherwise, the Si-Ag interface is corroded to be flat due to the strong corrosion capability of PbO, and the welding tension is too low. In addition, some extranet oxidation such as Li is added2The softening point of the O is adjusted to be in a proper range, so that the EL problem caused by overhigh softening point is avoided.
Class B glasses are still SiO2As network formers, but in relatively low amounts, SiO is avoided2Too high a content results in too high a softening point and contains a certain amount of TeO2，TeO2Has low melting point and extremely high flowing capacity, and is combined with a certain amount of exo-network oxide LiO2The B glass has moderate softening point and corrosion capacity, can be softened earlier and flows to a Si-Ag interface in the sintering process, and the contact time between the B glass and a Si substrate is increased, so that the corrosion is improved. The B glass can form better on a Si-Ag interfaceThe inverted pyramid structure increases the contact area, thereby providing better contact resistance and fill factor.
Class C glass with TeO2Is a main structure due to TeO2The silver-Ag-based high-temperature-resistant glass has very good fluidity and a low melting point, and simultaneously has a certain silver melting capacity, the silver melted into the liquid glass in the sintering process flows to the Si-Ag interface through gaps and is separated out when the temperature is reduced, so that the conductivity of the Si-Ag interface is increased, and the contact resistance is further reduced. Bi in C-type glass2O3Can provide a certain corrosion property to make the C glass contact with the Si substrate better, WO3The wettability with the silver powder can be increased, so that the silver powder can be better dissolved through TeO2-Bi2O3-WO3The proportion is adjusted to give the best properties for class C glasses.
According to one aspect of the embodiment of the invention, the glass frit for the solar cell conductive paste is a mixed glass frit composed of three types of glass A, B, C: a is PbO-SiO without tellurium oxide and bismuth oxide (and other oxides in bismuth valence state)2A glass system; b is SiO without lead oxide2-TeO2-Li2An O-oxide glass system; class C is TeO without lead oxide and silicon oxide2-Bi2O3-WO3An oxide glass system.
The A-type glass material comprises the following components in percentage by mole: SiO2220-60 mol%, PbO 25-80 mol%, Li2O content of 2 to 10 mol%, and 0 to 40 mol% of ZnO and WO3、Na2O、Al2O3CuO, MgO, or any of them. The B-type glass material comprises the following components in percentage by mole: SiO22The content of (A) is 10-50 mol%, TeO2In an amount of 2 to 24 mol%, Li2O content of 5 to 30 mol%, and 0 to 40 mol% of ZnO and WO3、Na2O、Al2O3CuO, MgO, or any of them. The C-type glass material comprises the following components in percentage by mole: TeO2The content of (a) is 90 to 95mol％，Bi2O3In an amount of 2 to 8 mol%, WO3The content of (a) is 1 to 7 mol%, and 0 to 8 mol% of ZnO and LiO2、Na2O、Al2O3CuO, MgO, or any of them. The oxides of zinc, tungsten, sodium, aluminum, copper and magnesium or the salts thereof play roles in further adjusting the softening point, and increasing the stability and acid and alkali resistance of the glass.
The glass material for the solar cell conductive paste can obtain better adhesive force and open pressure on a silicon chip, and simultaneously ensures lower contact resistance. In the mixed glass material, two types of glass materials do not contain heavy metal elements such as Pb and the like, so that the proportion of the heavy metal elements in the conductive silver paste is greatly reduced, and the industrial pollution is reduced. Meanwhile, the two Te series glass frits have different softening points, so that ohmic contact is ensured, and the solar cell has excellent electrical property.
In another aspect of the present invention, the preparation method of the glass frit for solar cell conductive paste includes a high temperature melting quenching method.
In some embodiments, the method of making the frit comprises: preparing raw materials according to the composition of the glass material for the solar cell conductive paste, mixing the raw materials uniformly, then melting at 900-1200 ℃ for 20-60 min, quenching the molten glass obtained by melting, then ball-milling and drying to obtain the glass material respectively, and thus obtaining the glass material for the solar cell conductive paste.
Further, the preparation method comprises the following steps: and mixing and homogenizing the raw materials of the glass frit by using a two-roll or three-roll mixer.
Further, the preparation method comprises the following steps: and carrying out the quenching treatment by adopting deionized water quenching or iron plate quenching.
Further, the preparation method comprises the following steps: and (3) carrying out ball milling by adopting a planetary ball mill.
Specifically, in some more specific embodiments, in the method for preparing the glass frit for solar cell conductive paste, the high-temperature melting quenching method includes the following steps:
taking one component raw material of the mixed glass frit, mixing and homogenizing the component raw material by a double-roller or three-roller mixer, transferring the mixture into a platinum crucible for melting, wherein the melting temperature is 900-1200 ℃, the melting time is 20-60 min, stirring the mixture in the melting process, and further homogenizing the mixture; and after the melting is finished, directly quenching the glass melt, quenching by using deionized water or an iron plate, and finally, ball-milling and drying by using a planetary ball mill to obtain the glass material.
The preparation method of the glass material for the solar cell conductive paste can be prepared by a high-temperature melting quenching method or a sol-gel method.
Another aspect of the embodiments of the present invention provides a solar cell conductive paste, which includes the following components in percentage by mass: 1-6% of the mixed glass material, 85-90% of silver and 6-11% of organic phase material.
Further, silver powder is used as the silver, but not limited thereto.
Further, the organic phase material is an organic phase generally used in the industry, and may be a combination of a silicone oil and an organic synthetic resin, but is not limited thereto.
Further, the organic synthetic resin may be any one or a combination of two or more of polyvinyl butyral, ethyl cellulose, propylene glycol butyl ether acetate, ethylene glycol butyl ether acetate, and the like, but is not limited thereto.
Another aspect of the embodiments of the present invention also provides a method for preparing the aforementioned solar cell conductive paste, including: and uniformly mixing the silver, the mixed glass material and the organic phase material to obtain the solar cell conductive paste.
In some embodiments, the method for preparing the conductive paste specifically comprises: the silver powder and the mixed glass material are premixed, the obtained mixture is added into the organic phase material and stirred for 1-2 hours, then the mixture is dispersed and homogenized on a three-roller machine, and when the fineness of a scraper is smaller than 10 mu m, the solar cell conductive paste is obtained.
Further, the preparation method for preparing the solar cell conductive paste comprises the following steps: taking the raw materials of the components, premixing the silver powder and the glass powder, adding the silver powder and the glass powder into the organic phase material, stirring for 1-2 hours, further dispersing and homogenizing the stirred raw materials on a three-roller machine, and finishing the preparation of the front silver paste when the fineness of a scraper is less than 10 microns.
The solar cell conductive paste has the characteristics of high open voltage, low series resistance, wider sintering window and higher tensile force.
The invention also provides application of the solar cell conductive paste in preparation of a single crystal PERC silicon wafer, a double-sided aluminum oxide single crystal silicon wafer, fine grids manufactured by single printing or fine grids manufactured by step-by-step printing.
The solar cell conductive paste can be applied to single printing and can also be applied to step-by-step printing to form fine grids, so that the process of different cell manufacturers is met. In addition, the conductive paste prepared by the glass material can be applied to a single-crystal PERC silicon chip and a double-sided aluminum oxide single-crystal silicon chip.
Correspondingly, the invention also provides a solar cell, which comprises the solar cell conductive paste.
In summary, according to the above technical scheme, the glass frit for the solar cell conductive paste of the present invention comprises an a-type glass frit without bismuth telluride, and further comprises B, C two types of tellurium-type glass frits with different softening temperatures, and through the matching use of A, B, C three types of glass frits, the glass frit has a strong silver melting capability, and simultaneously ensures a high open pressure, a low contact resistance and a high adhesive strength. The solar cell conductive paste can be applied to a single crystal PERC silicon wafer solar cell and a double-sided aluminum oxide single crystal silicon wafer.
It should be noted that the higher the on-voltage (also referred to as the open-circuit voltage, also referred to as Voc), the short-circuit current (Isc), and the fill factor (FF, the ratio of the maximum output power of the battery to the incident light power), the higher the conversion efficiency of the battery.
Note that, a difference of 0.02% or more between the battery conversion efficiencies is considered to be a difference between the two.
The technical solution of the present invention is further explained below with reference to several examples, but the present invention is not limited thereto. It is to be understood, however, that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with one another to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
The test methods described herein are conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
In this context, a range of values from one value to another is a general expression avoiding any recitation of all values in the range in the specification. Thus, recitation of a range of values herein is intended to encompass any value within the range and any smaller range defined by any value within the range, as if the range and smaller range were explicitly recited in the specification.
The invention will be further illustrated with reference to the following specific examples.
Comparative example 1
Step 1, preparing raw materials according to the following composition of the glass frit, and preparing the glass frit by adopting the method, wherein the melting temperature is 1100 ℃, and the melting time is 40 min.
The class A glass frit comprises the following components: 43 mol% SiO2、47mol％PbO、6mol％Li2O、4mol％Na2O。
The class B glass frit comprises the following components: 35 mol% SiO2、15mol％TeO2、20mol％Li2O、15mol％WO3、15mol％ZnO。
The class C glass frit comprises the following components: 91 mol% TeO2、4mol％Bi2O3、5mol％WO3。
Preparing conductive slurry: respectively preparing conductive paste by using A, B, C three types of glass frits prepared in the step 1, mixing 2.4 wt% of glass frits, 87.6 wt% of conductive silver powder, 3 wt% of polyvinyl butyral, 3 wt% of ethyl cellulose, 2 wt% of propylene glycol butyl ether acetate and 2 wt% of ethylene glycol monobutyl ether acetate organic phase for 1.5h, grinding the paste by using a three-roll grinder, and testing the grinding fineness by using a scraper plate fineness agent, wherein the grinding fineness of the paste is below 10 mu m. The front side silver paste slurry prepared from the glass frit in the type A is named as P1, the front side silver paste slurry prepared from the glass frit in the type B is named as P2, and the front side silver paste slurry prepared from the glass frit in the type C is named as P3.
Printing the prepared solar cell conductive paste P1, P2 and P3 on the front surface of a monocrystalline solar cell silicon wafer, drying and sintering the back surface of the monocrystalline solar cell silicon wafer by adopting uniform aluminum paste to prepare the solar cell, and testing the electrical property, wherein the average value of the results is shown in the following table I:
watch 1
As can be seen from table one, when the glass of class a is used alone as a glass frit for a solar cell, the prepared solar cell has a high open circuit voltage, but due to the insufficient corrosiveness of the glass of class a (high silica content), the series resistance is large and the filling is poor (small filling factor), and the EL problem is very easily caused. When the B-type glass and the C-type glass are independently used as glass frits of solar cells, the open-circuit voltage of the prepared solar cells is lower due to the strong corrosion capability and the good fluidity, and the comprehensive conversion efficiency is still poorer although the series resistance is smaller and the filling factor is larger. Therefore, although the A, B, C three types of glass frits have respective advantages, the frits are not suitable for being used alone for preparing the solar cell conductive paste.
Example 1
The glass type A, the glass type B and the glass type C in the comparative example 1 are prepared into mixed glass frits according to the proportion (wt%) of the following table II, and then the mixed glass frits are respectively used for preparing the conductive paste, specifically, 2.4 wt% of glass frits, 87.6 wt% of conductive silver powder, 3 wt% of polyvinyl butyral, 3 wt% of ethyl cellulose, 2 wt% of propylene glycol butyl ether acetate and 2 wt% of ethylene glycol butyl ether acetate are mixed for 1.5h, a three-roll grinder is used for grinding the paste, a scraper fineness agent is used for testing the grinding fineness, the grinding fineness of the paste is below 10 mu m, and the front silver paste is prepared, and the paste numbers are marked as P4-P7 and S1-S3.
Watch two
Printing the prepared solar cell conductive paste P4-P7 and S1-S3 on the front surface of a monocrystalline solar cell silicon wafer, drying and sintering the back surface of the monocrystalline solar cell silicon wafer by adopting uniform aluminum paste to prepare the solar cell, and testing the electrical property, wherein the average value of the results is shown in the following table III:
watch III
In the embodiment, the solar cell conductive paste prepared by mixing A, B, C types of glass frits according to a certain proportion has better open-circuit voltage, contact resistance and filling factor, and the comprehensive efficiency is optimal. As can be seen from paste numbers P4-P7, the three types A, B, C of glass frits have a certain synergistic effect in the preparation of conductive silver paste, compared with the paste numbers P1-P3. The comparison between P4 and P5 shows that, as the quality of the class a frit increases, the usage amount of the class B, C glass decreases, the open-circuit voltage increases, and the open-circuit advantage becomes more and more obvious, but the series resistance is larger, the filling factor is smaller, and the corrosion capability gradually decreases. Referring to S2, when the amount of the glass frit in class a is increased, the obtained solar cell has a high on-voltage but a large series resistance, and the comprehensive electrical properties cannot meet the requirements.
The comparison between P5 and P6 and P7 shows that with the increase of the B-type frit or C-type frit, the advantages of the series resistance and the fill factor become more and more obvious (the series resistance decreases and the fill factor increases), and the interaction between the B-type glass and the C-type glass needs to have certain corrosivity and sufficient silver dissolving capacity, so that the combination can ensure that the series resistance and the fill factor are better.
When the amount of the type B frit or the type C frit is relatively high, as in the paste designation S1, the content of the type B frit is high, and the open-circuit voltage performance of the prepared solar cell is not ideal, which is close to that of a solar cell prepared by using the type B frit alone. In the paste label S3, the content of C-type glass frit is high, the open circuit voltage and the series resistance of the prepared solar cell are not ideal, and the comprehensive electrical property cannot meet the requirement.
Example 3 preparation of solar cell front side silver paste P8
Step 1, preparing raw materials according to the following composition of the glass frit, and preparing the glass frit by adopting the method, wherein the melting temperature is 1150 ℃, and the melting time is 50 min.
The class A glass frit comprises the following components: 50 mol% SiO2、40mol％PbO、5mol％Li2O、3mol％Na2O、2mol％ZnO。
The class B glass frit comprises the following components: 45 mol% SiO2、10mol％TeO2、15mol％Li2O、10mol％Na2O、10mol％WO3、10mol％ZnO。
The class C glass frit comprises the following components: 93 mol% TeO2、2mol％Bi2O3、3mol％WO3、2mol％Li2O。
Step 2: and (2) preparing the A-type glass frit, the B-type glass frit and the C-type glass frit prepared in the step (1) into a mixed glass frit, wherein the A-type glass accounts for 40% by mass, the B-type glass accounts for 40% by mass and the C-type glass accounts for 20% by mass. A solar cell conductive paste was prepared in a similar manner to example 1, and the resulting front side silver paste was designated P8.
Example 4 preparation of solar cell front side silver paste P9
Step 1, preparing raw materials according to the following composition of the glass frit, and preparing the glass frit by adopting the method, wherein the melting temperature is 1000 ℃, and the melting time is 50 min.
The class A glass frit comprises the following components: 30 mol% SiO2、60mol％PbO、3mol％Li2O、3mol％ZnO、2mol％Na2O、2mol％CuO。
The class B glass frit comprises the following components: 30 mol% SiO2、20mol％TeO2、15mol％WO3、15mol％ZnO、12mol％Li2O、8mol％Na2O。
The class C glass frit comprises the following components: 95 mol% TeO2、2mol％Bi2O3、2mol％WO3、1mol％Li2O。
And 2, preparing the A-type glass frit, the B-type glass frit and the C-type glass frit which are prepared in the step 1 into mixed glass frit, wherein the A-type glass accounts for 40% by mass, the B-type glass accounts for 40% by mass and the C-type glass accounts for 20% by mass.
3.0 wt% of mixed glass material, 91 wt% of conductive silver powder, 3 wt% of polyvinyl butyral and 3 wt% of ethyl cellulose are mixed for 1.5h, the slurry is ground by a three-roll grinder, the grinding fineness is tested by a scraper plate fineness agent, the grinding fineness of the slurry is below 10 mu m, and the prepared front silver slurry is named as P9.
Example 5 preparation of solar cell front side silver paste P10
Step 1, preparing raw materials according to the following composition of the glass frit, and preparing the glass frit by adopting the method, wherein the melting temperature is 1100 ℃, and the melting time is 50 min.
The class A glass frit comprises the following components: 35 mol% SiO2、50mol％PbO、5mol％Li2O、5mol％WO3、3mol％ZnO、1mol％Na2O、1mol％CuO。
The class B glass frit comprises the following components: 30 mol% SiO2、23mol％TeO2、15mol％WO3、15mol％ZnO、10mol％Li2O、7mol％Na2O。
The class C glass frit comprises the following components: 90 mol% TeO2、8mol％Bi2O3、1mol％WO3、0.5mol％Li2O and 0.5 mol% ZnO, and preparing according to the method in the step 1 to obtain the C-type glass material.
And 2, preparing the A-type glass frit, the B-type glass frit and the C-type glass frit which are prepared in the step 1 into a mixed glass frit, wherein the A-type glass accounts for 40% by mass, the B-type glass accounts for 40% by mass and the C-type glass accounts for 20% by mass.
Mixing 4.0 wt% of mixed glass frit, 85 wt% of conductive silver powder, 3 wt% of polyvinyl butyral, 3 wt% of ethyl cellulose, 2 wt% of propylene glycol butyl ether acetate and 3 wt% of ethylene glycol butyl ether acetate for 1 hour, grinding the slurry by using a three-roll grinder, testing the grinding fineness by using a scraper fineness agent, and setting the grinding fineness of the slurry to be less than 10 microns, wherein the prepared front silver paste slurry is named as P10.
Example 6 preparation of solar cell front side silver paste P11
Step 1, preparing raw materials according to the following composition of the glass frit, and preparing the glass frit by adopting the method, wherein the melting temperature is 1150 ℃, and the melting time is 45 min.
The class A glass frit comprises the following components: 20 mol% SiO2、78mol％PbO、2mol％Li2O。
The class B glass frit comprises the following components: 20 mol% SiO2、18mol％TeO2、22mol％WO3、13mol％Bi2O3、20mol％Li2O、7mol％ZnO。
The class C glass frit comprises the following components: 94 mol% TeO2、3mol％Bi2O3、1mol％WO3、1mol％Li2O、1mol％ZnO。
And 2, preparing the A-type glass frit, the B-type glass frit and the C-type glass frit which are prepared in the step 1 into a mixed glass frit, wherein the A-type glass accounts for 40% by mass, the B-type glass accounts for 40% by mass and the C-type glass accounts for 20% by mass.
Mixing 1.5 wt% of mixed glass frit, 88.5 wt% of conductive silver powder, 3 wt% of polyvinyl butyral, 3 wt% of ethyl cellulose, 1 wt% of propylene glycol butyl ether acetate and 3 wt% of ethylene glycol butyl ether acetate for 1 hour, grinding the slurry by using a three-roll grinder, testing the grinding fineness by using a scraper fineness agent, wherein the grinding fineness of the slurry is below 10 mu m, and the prepared front silver paste slurry is named as P11.
Example 7 preparation of solar cell front side silver paste P12
Step 1, preparing raw materials according to the following composition of the glass frit, and preparing the glass frit by adopting the method, wherein the melting temperature is 1150 ℃, and the melting time is 50 min.
The class A glass frit comprises the following components: 60 mol% SiO2、25mol％PbO、10mol％Li2O、3mol％Na2O、2mol％ZnO。
The class B glass frit comprises the following components: 42 mol% SiO2、14mol％TeO2、17mol％Li2O、10mol％Na2O、10mol％WO3、7mol％ZnO。
The class C glass frit comprises the following components: 91 mol% TeO2、8mol％Bi2O3、1mol％WO3。
And 2, preparing the A-type glass frit, the B-type glass frit and the C-type glass frit which are prepared in the step 1 into a mixed glass frit, wherein the A-type glass accounts for 40% by mass, the B-type glass accounts for 40% by mass and the C-type glass accounts for 20% by mass. Referring again to the method of example 1, a front side silver paste slurry was prepared and the prepared front side silver paste slurry was designated P12.
Example 8 preparation of solar cell front side silver paste P13
Step 1, preparing raw materials according to the following composition of the glass frit, and preparing the glass frit by adopting the method, wherein the melting temperature is 1150 ℃, and the melting time is 50 min.
The class A glass frit comprises the following components: 53 mol% SiO2、25mol％PbO、10mol％Li2O、8mol％Na2O、4mol％ZnO。
The class B glass frit comprises the following components: 10 mol% SiO2、24mol％TeO2、30mol％Li2O、16mol％Na2O、10mol％WO3、10mol％ZnO。
The class C glass frit comprises the following components: 92 mol% TeO2、7mol％Bi2O3、1mol％WO3。
And 2, preparing the A-type glass frit, the B-type glass frit and the C-type glass frit which are prepared in the step 1 into a mixed glass frit, wherein the A-type glass accounts for 40% by mass, the B-type glass accounts for 40% by mass and the C-type glass accounts for 20% by mass. Referring again to the method of example 1, a front side silver paste slurry was prepared and the prepared front side silver paste slurry was designated P13.
Example 9 preparation of solar cell front side silver paste P14
Step 1, preparing raw materials according to the following composition of the glass frit, and preparing the glass frit by adopting the method, wherein the melting temperature is 1150 ℃, and the melting time is 50 min.
The class A glass frit comprises the following components: 51 mol% SiO2、44mol％PbO、4mol％Li2O、1mol％Na2O。
The class B glass frit comprises the following components: 50 mol% SiO2、2mol％TeO2、8mol％Li2O、20mol％Na2O、10mol％WO3、10mol％ZnO。
The class C glass frit comprises the following components: 91 mol% TeO2、2mol％Bi2O3、7mol％WO3。
And 2, preparing the A-type glass frit, the B-type glass frit and the C-type glass frit which are prepared in the step 1 into a mixed glass frit, wherein the A-type glass accounts for 40% by mass, the B-type glass accounts for 40% by mass and the C-type glass accounts for 20% by mass. Referring again to the method of example 1, a front side silver paste slurry was prepared and the prepared front side silver paste slurry was designated P14.
Example 10 preparation of solar cell front side silver paste S4
Step 1, preparing raw materials according to the following composition of the glass frit, and preparing the glass frit by adopting the method, wherein the melting temperature is 1000 ℃, and the melting time is 50 min.
The A-type glass material comprises the following components: 10 mol% SiO2、82mol％PbO、4mol％Li2O、2mol％ZnO、1mol％MgO、1mol％CuO。
The class B glass frit comprises the following components: 8 mol% SiO2、40mol％TeO2、40mol％WO3、8mol％ZnO、2mol％Li2O、2mol％Na2O。
The class C glass frit comprises the following components: 80mol％TeO2、15mol％Bi2O3、3mol％WO3、2mol％Li2O。
And 2, preparing the A-type glass frit, the B-type glass frit and the C-type glass frit which are prepared in the step 1 into a mixed glass frit, wherein the A-type glass accounts for 40% by mass, the B-type glass accounts for 40% by mass and the C-type glass accounts for 20% by mass. Referring again to the method of example 1, a front side silver paste slurry was prepared and the prepared front side silver paste slurry was designated as S4.
Example 11 preparation of solar cell front side silver paste S5
Step 1, preparing raw materials according to the following composition of the glass frit, and preparing the glass frit by adopting the method, wherein the melting temperature is 1000 ℃, and the melting time is 50 min.
The class A glass frit comprises the following components: 70 mol% SiO2、25mol％PbO、4mol％Li2O、1mol％ZnO。
The class B glass frit comprises the following components: 55 mol% SiO2、40mol％TeO2、5mol％WO3。
The class C glass frit comprises the following components: 96 mol% TeO2、3mol％Bi2O3、1mol％WO3。
And 2, preparing the A-type glass frit, the B-type glass frit and the C-type glass frit which are prepared in the step 1 into a mixed glass frit, wherein the A-type glass accounts for 40% by mass, the B-type glass accounts for 40% by mass and the C-type glass accounts for 20% by mass. Referring again to the method of example 1, a front side silver paste slurry was prepared and the prepared front side silver paste slurry was designated as S5.
Comparative example 2
A Pb-Si-Te-Bi glass frit A1 for a conventional commercial solar cell conductive paste was purchased, 2.4 wt% of A1 glass frit, 87.6 wt% of conductive silver powder, 3 wt% of polyvinyl butyral, 3 wt% of ethyl cellulose, 2 wt% of propylene glycol butyl ether acetate, and 2 wt% of ethylene glycol monobutyl ether acetate were mixed in an organic phase for 1.5 hours, the paste was ground using a three-roll grinder, the grinding fineness was measured using a blade fineness agent, the grinding fineness of the paste was below 10 μm, and the obtained front side silver paste was named S6.
The Pb-Si-Te-Bi glass frit a2 for a conventional commercial solar cell conductive paste was purchased and the front side silver paste was prepared according to the method described above and named S7.
The Pb-Si-Te-Bi glass frit a3 for a conventional commercial solar cell conductive paste was purchased and the front side silver paste was prepared according to the method described above and named S8.
The Pb-Si-Te-Bi glass frit a4 for a conventional commercial solar cell conductive paste was purchased and the front side silver paste was prepared according to the method described above and named S9.
The Pb-Si-Te-Bi glass frit a5 for a conventional commercial solar cell conductive paste was purchased and the front side silver paste was prepared according to the method described above and named S10.
Example 12 Performance testing
The front side silver paste pastes prepared in examples 3 to 11 and comparative example 2 were used to prepare solar cells, respectively, according to the method of example 1, and the performance of the solar cells was tested, and the results are shown in table four:
watch four
Based on the example 2, the mixture ratio of the components in the A, B, C three types of glass frits is further adjusted, so that the content of silicon oxide in the A type of glass frits is 20-60 mol%, the content of lead oxide is 25-80 mol%, and the content of lithium oxide is 2-10 mol%. The content of silicon oxide in the B-type glass frit is 10-50 mol%, the content of tellurium oxide is 2-24 mol%, and the content of lithium oxide is 5-30 mol%. The content of tellurium oxide in the C-type glass frit is 90-95 mol%, the content of bismuth oxide is 2-8 mol%, and the content of tungsten oxide is 1-7 mol%. Referring to the paste number P8-P14, the prepared solar cell has relatively high open-circuit voltage, short-circuit current and filling factor, relatively low contact resistance and comprehensive electrical property meeting the requirements.
Further, the conductive paste prepared in the above examples has better overall electrical properties and higher conversion efficiency than the commercially available glass frits in paste numbers S6-S10.
Example 13 tensile testing
One sheet was taken out of each of the solar cells prepared by paste No. P4 in example 2 and paste nos. P8 and P9 in examples 3 and 4 and paste nos. S7, S8 and S10 in comparative example 2, and a tensile test was performed, and the tensile test results are shown in table five.
Watch five
| P4 | P8 | P9 | S7 | S8 | S10 | |
| tension/N | 3.3 | 3.1 | 3.0 | 2.9 | 2.5 | 2.8 |
As can be seen from the above table, the conductive paste of the above embodiment has a higher tensile force, and the tensile force performance is even higher than that of the existing glass.
In conclusion, the solar cell prepared from the glass material for the solar cell conductive paste has better ohmic contact, higher conversion efficiency and higher bonding strength, and can achieve the design purpose of the invention. Therefore, the glass frit provided by the invention is used for preparing the conductive paste, so that the conductive paste obtains excellent electrical property and higher tensile force.
While the foregoing is directed to the preferred embodiment of the present invention, it is not intended to detail all of the same, and it is to be understood that such embodiment is merely illustrative of the present invention and is not to be considered as limiting the scope of the invention, which is limited only by the claims and their full scope and equivalents.
The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. In light of the above teachings, those skilled in the art will readily appreciate that the materials and their equivalents, the processes and their equivalents, as listed or exemplified herein, are capable of performing the invention in any of its several forms, and that the upper and lower limits of the parameters of the materials and processes, and the ranges of values between these limits are not specifically enumerated herein.
Claims (11)
1. A glass material for solar cell conductive paste is characterized in that the glass material is a mixed glass material composed of A, B, C three types of glass, wherein,
class A is a Pb-Si glass system free of tellurium and bismuth; the B type is a lead-free Si-Te-Li glass system; class C is a Te-Bi-W glass system that is lead and silicon free.
2. The frit according to claim 1, wherein the group a frit comprises 30% to 70% of the total mass of the mixed frit, the group B frit comprises 20% to 60% of the total mass of the mixed frit, and the group C frit comprises 5% to 40% of the total mass of the mixed frit.
3. The glass frit according to claim 1 or 2, wherein the group a glass frit contains 20 to 60 mol% of silicon oxide, 25 to 80 mol% of lead oxide, and 2 to 10 mol% of lithium oxide in terms of oxide.
4. The glass frit according to claim 1 or 2, wherein the group B glass frit contains, in terms of oxide, 10 to 50 mol% of silicon oxide, 2 to 24 mol% of tellurium oxide, and 5 to 30 mol% of lithium oxide.
5. The glass frit according to claim 1 or 2, wherein the content of tellurium oxide is 90 to 95 mol%, the content of bismuth oxide is 2 to 8 mol%, and the content of tungsten oxide is 1 to 7 mol%, in terms of oxide, of the C-type glass frit.
6. The frit according to claim 1 or 2, wherein the group a glass or the group B glass further comprises one or any of oxides of zinc, tungsten, sodium, aluminum, copper, magnesium or salts thereof; preferably, the total amount of the oxides of zinc, tungsten, sodium, aluminum, copper, magnesium or salts thereof is 0 to 42 mol%.
7. The glass frit according to claim 1 or 2, wherein the group C glass further comprises one or any of oxides of zinc, lithium, sodium, aluminum, copper, magnesium, or salts thereof; preferably, the total amount of the oxides of zinc, lithium, sodium, aluminum, copper, magnesium or salts thereof is 0 to 8 mol%.
8. The method for preparing a glass frit for a solar cell conductive paste according to any one of claims 1 to 7, comprising: the material is prepared by a high-temperature melting quenching method or a sol-gel method;
preferably, the preparation method comprises the following steps: preparing raw materials according to the composition of the glass frit for the solar cell conductive paste as defined in any one of claims 1 to 7, respectively, uniformly mixing the raw materials, melting at 900-1200 ℃ for 20-60 min, quenching, ball-milling, and drying to obtain the glass frit respectively.
9. The solar cell conductive paste, which is characterized by comprising the mixed glass of any one of claims 1 to 7 or the glass frit prepared by the preparation method of claim 8 or 9, wherein the content of the mixed glass frit is controlled to be 1 to 6 percent by mass.
10. Use of the glass frit for solar cell conductive paste according to any one of claims 1 to 7, or the glass frit prepared by the preparation method according to claim 8, or the glass frit for solar cell conductive paste according to claim 9 for preparing a single-crystal PERC silicon wafer, a double-sided alumina single-crystal silicon wafer, a single-pass printing for manufacturing a fine grid, or a step printing for manufacturing a fine grid.
11. A solar cell prepared from the electroconductive paste according to claim 10.
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